Magnesium pyrophosphate phosphor



Patented Nov. 22, 1949 at FICE MAGNESIUM PYROPHOSPHATE PHOSPHOR Herman C. Froelich, Cleveland Heights, Ohio, as-

signor to General Electric Company, a corporation of New Kori;

No Brawing. Application April 15, 1947, Serial No. 741,693

3 Elairns.

My invention relates to phosphors, that is, fluorescent or phosphorescent compositions.

In my application Se" ial No. 741,692, now Patent 2,455,415, of even date, I disclose and claim a phosphor consisting of a matrix of magnesium phosphate, preferably of pyrophosphate composition, activated by both trivalent cerium and thorium, and emitting ultraviolet radiations of longer Wave length when excited by ultraviolet radiations of shorter wave length.

According to the present invention, I have discovered that the addition of manganese as a third activator to the cerium and thorium activated magnesium pyrophosphate phosphor results in an entirely new series of phosphors. They respond to excitation by radiation of 2537 A. with the emission of varying shades of light, depending upon the composition. The colors produced range from light green to deep orange, plus small amounts of ultraviolet radiation and blue light.

phors having high thorium content is generally greater.

The shape of the emission curves in the visible is about the same for all colors, but the peak can be shifted from 5&60 to 5950 A. and possibly A phosphor of magnesium pyrophosphate acti- Mgzpzorl llvrols vated with manganese alone does not respond t0 C6203 001 2 2537 A. excitation, but gives green-yellow to T1102 orange light when excited With cathode rays, (18- Mno o pending upon the manganese concentration. 1 to .8

Magnesium pyrophosphate double activated with either cerium-manganese or thorium -manganese alone, likewise does not respond more than faintl to 2537 A. excitation with the emission Although the activators are most likely present as phosphates, their concentrations have been given in terms of oxide.

It is at present not clear just Why the triple of visible radiations. The cathode ray response so activation is e es ry n how he lem ntary of these phosphors is governed primarily by the acts of absorption, energy transfer and emission manganese Concentration giving mostly orange are tied up with the nature of the different acshades. tivators. It seems clear that not all manganese The triple activated phosphors comprising the atoms, for example, can participate equally in the present invention have, in general, an emission emission act, else the color and brightness uld spectrum consisting of three bands. One band is not depend upon the thorium concentration For in the ultraviolet with a peak near 3500 A. The this reason, I referred above to efiective m int y of this band decreases With in re ganese concentration. Elfective and absolute concentrations of thorium and mallgallesa The manganese concentration become identical only inte j Of t illimvlolet baud Only F few at very high concentrations of thorium. It apper cent in thobrlgl'lesll phcsphoTS-g T 1 1s pears as though the number of cerium atoms may a blu P wllih a peak Its be appreciably lower than the number of mantensity is likewise low. There IS a third strong ganese atoms band m h Vlslble Whlch 1S a i 9} In the ultraviolet emitting magnesium pyroplex and 1S determined by the effective manh Uh t h h 1 ganese concentration. The effective man- 9 p osp Ors also Osed m copeehng ganese concentration is equal to or lower than its 3919110335.? referred F abOVQ, thollll'm ensltlzed absolute concentration, and depends also upon the the efmsslon of cenumsmce nfilther of w concentration of thorium. Within reason, it does combmations Ce-Mn Th'Mn 1n the matnx net seem to depend upon the Cerium concentmresponded to 2537 A. excitation, I choose to refer tion. Thus, the same color of orange may be obtained with a low concentration of manganese and high thorium, compared with high manganese and low thorium at a given concentration of cerium. However, the brightness of the phosto the phenomenon of Ce-Th-Mn activation as an induced fluorescence. It is not known at the present time whether it is brought about by a change of field in the matrix, thus inducing the Mn to fluoresce where it normally would not, or

whether there is an internal cascade transfer of radiant energy inducing the Mn to fluoresce.

The phosphors comprising my invention respond to 3650 A. excitation with a Weak emission in the deep red. The position of the peak does not seem to be aifected by the concentration of any of the activators, but its intensity increases with the Mn concentration, up to a maximum. Thus the invention makes available some highly unusual phosphors which fiuoresce deep red under long ultraviolet excitation, and yellow or green under short ultraviolet excitation.

The phosphor may be prepared by cold coprecipitation of magnesium, cerium, thorium and. manganese phosphates as magnesium ammonium phosphate plus activators, and firing at temperatures of about 9001200 0., preferably 1100 C., in an atmosphere of steam and hydrogen. More particularly, a suitable phosphor may be prepared in accordance with the following specific example: 255 grams Mg(NO3)zX6H2O, 7 grams Ce(NO3)3X6I-I20, 35 grams Th(NO3)44H2O, and. 10 cc. of a 50% manganese nitrate solution are dissolved in 1 liter of cold distilled water. To this is added, under vigorous stirring, a solution of 200 grams (NH4)2HPO4 in 1 liter of water, followed by 200 cc. of concentrated ammonia. After some standing, the crystalline precipitate is filtered off, Washed, dried, sieved, then fired in hydrogen and steam for 1 hr. at 1100 C. After cooling in hydrogen, the phosphor is sieved and then ready for use. Other methods of preparations may be followed.

In the above example the calculated composition is one mol MgzPzO-z to .016 mol CezOs, .127 mol ThOz and .084 mol MnO.

No other third activator in place of manganese has been found to be effective. Neither was any advantage obtained by adding manganese to cerium and thorium activated phosphates of calcium, aluminum and strontium. Also, compositions of orthophosphate proportions are definitely less bright than the pyrophosphate composition, and compositions more basic than orthophosphate were almost non-fluorescent.

The addition of comparatively small amounts of silica, say up to about 10%, improved the friability of the phosphor. While a nominal amount as low as 001% may be used, I prefer to use about 1 to 5% of silica.

The phosphor may be used as a coating on the inner surface of the envelope of a loW pressure mercury discharge lamp such as those now commercially well-known.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. A fluorescent composition consisting essentially of magnesium pyrophosphate activated by cerium, thorium and magnanese in approximately the range of proportions of 1 mol Mg2P2O'I, .001 to 0.2 mol CezOs, .001 to 0.5 mol ThOz and .01 to 0.8 mol MnO.

2. A fluorescent composition consisting essentially of magnesium pyrophosphate activated by cerium, thorium and manganese in approximately the range of proportions of 1 mol Mg2P2O7, .001 to 0.2 mol CezOs, .001 to 0.5 mol ThO2 and .01 to 0.8 mol MnO, and about .001-10% of silica.

3. A fluorescent composition consisting essentially of mangesium pyrophosphate activated by cerium, thorium and manganese in proportions of about 1 mol Mg2P207 to .016 mol CezOa, .127 mol T1102 and .084 mol MnO.

HERMAN C. FROELICH.

REFERENCES CITED UNITED STATES PATENTS Name Date Fischer Aug. 4, 1936 Number 

